Theoretical model of femtosecond coherence spectroscopy of vibronic excitons in molecular aggregates.

When used as pump pulses in transient absorption spectroscopy measurements, femtosecond laser pulses can produce oscillatory signals known as quantum beats. The quantum beats arise from coherent superpositions of the states of the sample and are best studied in the Fourier domain using Femtosecond Coherence Spectroscopy (FCS), which consists of one-dimensional amplitude and phase plots of a specified oscillation frequency as a function of the detection frequency. Prior works have shown ubiquitous amplitude nodes and π phase shifts in FCS from excited-state vibrational wavepackets in monomer samples.

Spatiotemporal dispersion compensation for a 200-THz noncollinear optical parametric amplifier.

A noncollinear optical parametric amplifier (NOPA) can produce few-cycle femtosecond laser pulses that are ideally suited for time-resolved optical spectroscopy measurements. However, the nonlinear-optical process giving rise to ultrabroadband pulses is susceptible to spatiotemporal dispersion problems. Here, we detail refinements, including chirped-pulse amplification (CPA) and pulse-front matching (PFM), that minimize spatiotemporal dispersion and thereby improve the properties of ultrabroadband pulses produced by a NOPA.

Perturbative theoretical model of electronic transient circular dichroism spectroscopy of molecular aggregates.

A chiral analog of transient absorption spectroscopy, transient circular dichroism (TCD) spectroscopy is an emerging time-resolved method. Both spectroscopic methods can probe the electronic transitions of a sample, and TCD is additionally sensitive to the dynamic aspects of chirality, such as those induced by molecular excitons. Here, we develop a theoretical description of TCD for electronic multi-level models in which the pump pulse is linearly polarized and probe pulse is alternately left- and right-circularly polarized.

Characterizing Mode Anharmonicity and Huang-Rhys Factors Using Models of Femtosecond Coherence Spectra.

Femtosecond laser pulses readily produce coherent quantum beats in transient-absorption spectra. These oscillatory signals often arise from molecular vibrations and therefore may contain information about the excited-state potential energy surface near the Franck-Condon region. Here, by fitting the measured spectra of two laser dyes to microscopic models of femtosecond coherence spectra (FCS) arising from molecular vibrations, we classify coherent quantum-beat signals as fundamentals or overtones and quantify their Huang-Rhys factors and anharmonicity values.

Independent learning of the sonographic FAST exam technique using a tablet-based training module.

Objective: The aim of this study is to determine if a specific tablet-based training module can be used as an effective tool for independently training novice sonographers in the components of the focused assessment for sonography in trauma (FAST) exam.

Design: Participants attended a 15-minute orientation presentation followed by a 2-hour ultrasound scanning workshop where they used a novel tablet-based training module to learn the components of the FAST exam independently.

Setting: This study took place at an accredited United States college of osteopathic medicine.

Signatures of Vibrational and Electronic Quantum Beats in Femtosecond Coherence Spectra.

Femtosecond laser pulses can produce oscillatory signals in transient-absorption spectroscopy measurements. The quantum beats are often studied using femtosecond coherence spectra (FCS), the Fourier domain amplitude, and phase profiles at individual oscillation frequencies. In principle, one can identify the mechanism that gives rise to each quantum-beat signal by comparing its measured FCS to those arising from microscopic models.

Broad-Band Pump-Probe Spectroscopy Quantifies Ultrafast Solvation Dynamics of Proteins and Molecules.

In this work, we demonstrate the use of broad-band pump-probe spectroscopy to measure femtosecond solvation dynamics. We report studies of a rhodamine dye in methanol and cryptophyte algae light-harvesting proteins in aqueous suspension. Broad-band impulsive excitation generates a vibrational wavepacket that oscillates on the excited-state potential energy surface, destructively interfering with itself at the minimum of the surface.

Progression of moderate-to-severe carotid disease.

Objective: Our goals were to investigate the degree to which patient demographics, risk factors, laboratory data, and medications influence moderate carotid disease progression among patients with asymptomatic moderate carotid disease and whether such associations are solely based on how progression is defined. In addition, we aimed to establish optimal threshold criteria to categorize patients at high risk of progression.

Methods: In this retrospective study, 621 arteries were evaluated for internal carotid artery (ICA) stenosis between January 1997 and January 2014 and were determined to have moderate (50%-79%) stenosis via color duplex ultrasonography.

Spectroscopic Studies of Cryptophyte Light Harvesting Proteins: Vibrations and Coherent Oscillations.

The first step of photosynthesis is the absorption of light by antenna complexes. Recent studies of light-harvesting complexes using two-dimensional electronic spectroscopy have revealed interesting coherent oscillations. Some contributions to those coherences are assigned to electronic coherence and therefore have implications for theories of energy transfer.

Coherent oscillations in the PC577 cryptophyte antenna occur in the excited electronic state.

Transient absorption spectroscopy is a useful measurement for investigating ultrafast dynamics in molecules. We have developed a transient absorption spectrometer that utilizes balanced and fast detection methods to suppress noise and maintain high temporal and spectral resolution. We use the spectrometer to investigate the ultrafast dynamics in a photosynthetic pigment-protein complex, the phycobiliprotein PC577 isolated from the cryptophyte alga Hemiselmis pacifica CCMP706.

Photosynthetic light harvesting: excitons and coherence.

Photosynthesis begins with light harvesting, where specialized pigment-protein complexes transform sunlight into electronic excitations delivered to reaction centres to initiate charge separation. There is evidence that quantum coherence between electronic excited states plays a role in energy transfer. In this review, we discuss how quantum coherence manifests in photosynthetic light harvesting and its implications.

Coherent multidimensional optical spectra measured using incoherent light.

Four-wave mixing measurements can reveal spectral and dynamics information that is hidden in linear spectra by the interactions among light-absorbing molecules and with their environment. Coherent multidimensional optical spectroscopy is an important variant of four-wave mixing because it resolves a map of interactions and correlations between absorption bands. Previous coherent multidimensional optical spectroscopy measurements have used femtosecond pulses with great success, and it may seem that femtosecond pulses are necessary for such measurements.

Direct visualization of laser-driven electron multiple scattering and tunneling distance in strong-field ionization.

Using a simple model of strong-field ionization of atoms that generalizes the well-known 3-step model from 1D to 3D, we show that the experimental photoelectron angular distributions resulting from laser ionization of xenon and argon display prominent structures that correspond to electrons that pass by their parent ion more than once before strongly scattering. The shape of these structures can be associated with the specific number of times the electron is driven past its parent ion in the laser field before scattering. Furthermore, a careful analysis of the cutoff energy of the structures allows us to experimentally measure the distance between the electron and ion at the moment of tunnel ionization.

Bright coherent ultrahigh harmonics in the keV x-ray regime from mid-infrared femtosecond lasers.

High-harmonic generation (HHG) traditionally combines ~100 near-infrared laser photons to generate bright, phase-matched, extreme ultraviolet beams when the emission from many atoms adds constructively. Here, we show that by guiding a mid-infrared femtosecond laser in a high-pressure gas, ultrahigh harmonics can be generated, up to orders greater than 5000, that emerge as a bright supercontinuum that spans the entire electromagnetic spectrum from the ultraviolet to more than 1.6 kilo-electron volts, allowing, in principle, the generation of pulses as short as 2.

Bright, coherent, ultrafast soft X-ray harmonics spanning the water window from a tabletop light source.

We demonstrate fully phase-matched high harmonic emission spanning the water window spectral region important for nano- and bioimaging and a breadth of materials and molecular dynamics studies. We also generate the broadest bright coherent bandwidth (≈300  eV) to date from any light source, small or large, that is consistent with a single subfemtosecond burst. The harmonic photon flux at 0.

Spatially coherent, phase matched, high-order harmonic EUV beams at 50 kHz.

By focusing a high repetition rate (50 kHz), compact, femtosecond laser system with low pulse energy (25 muJ) using a tight-focusing geometry, we demonstrate fully phase matched high-order harmonic generation for the first time at very high repetition rates, resulting in EUV light with full spatial coherence. The result is a practical, single-box, coherent source useful for applications in metrology, ultrafast spectroscopy, imaging and microscopy. The soft x-ray flux can be improved further by increasing the laser pulse energy and/or repetition rate.

Enhanced high harmonic generation from multiply ionized argon above 500 eV through laser pulse self-compression.

By combining laser pulse self-compression and high harmonic generation within a single waveguide, we demonstrate high harmonic emission from multiply charged ions for the first time. This approach enhances the laser intensity and counteracts ionization-induced defocusing, extending the cutoff photon energy in argon above 500 eV for the first time, with higher spectral intensity and cutoff energy than He for the same input laser parameters. This Letter demonstrates a pathway for extending high harmonic emission to very high photon energies using large, multiply charged, ions with high ionization potentials.

Quasi-phase matching of high-order harmonic generation at high photon energies using counterpropagating pulses.

We extend all-optical quasi-phase matching of high-order harmonic generation into spectral regions where conventional phase matching is not possible. The high laser intensities required to generate harmonics at energy >130 eV, coupled with the resulting high level of ionization, preclude conventional phase matching in all nonlinear media. Selective enhancement factors between 40 and 150 in the flux of harmonics at photon energies around 140 eV are demonstrated using a train of two counterpropagating pulses.